Sorbitol ethers



twice with about 75 cc. of benzene.

Patented Nov. 21, 1933 UNITED STATES PATENT OFFICE SORBITOL ETHERS No Drawing. Application October 17, 1930 Serial No. 489,483 I 11 Claims.

object is the preparation of new compositions of matter, such as coating and plastic compositions comprised of these ethers.

These objects are accomplished by the following preferred mode of procedure in which an alkyl or aryl halide is reacted with sorbitol in the presence of a basic material, and preferably in the presence of a diluent.

Sorbitol, which may be prepared by the reduction of glucose, is readily soluble in water but is only slightly soluble in hydrocarbons and in various other lacquer solvents. These properties make sorbitol of little value for use as a plasticizer in coating compositions. I have discovered, however, that it is possible to prepare new compounds having properties widely different from that of sorbitol, and that the new compounds are practically insoluble in water, but are soluble in organic solvents for use in coating and plastic compositions.

More specifically I have found that the replacement of hydroxyl groups in sorbitol with ether groups (alkoxy or aryloxy groups) yields products which are soluble in lacquer solvents, and which are much less' soluble in water than is sorbitol. The number of hydroxyl groups which it is necessary to replace with ether groups to secure products substantially insoluble in water, is dependent upon the particular ether groups introduced. For example, the introduction of phenoxy groups is more effective in producing water insolubility than is the introduction of methoxy groups.

The following examples are illustrative of the preferred mode of preparing these ethers:

Example 1 A mixture of 250 g. crude sorbitol, 400 g. ethyl chloride, 248 g. sodium hydroxide, 40 g. water, and 550 g. benzene was heated in a nickel autoclave with stirring for five hours at 140-155 C. When the mixture reached room temperature, it was removed from the autoclave and filtered. The residue obtained in the filtration was washed The benzene layer of the filtrate and the benzene solution obtained by extracting the water layer with 250 cc. of benzene were combined and heated on a steam bath to remove the benzene, ethyl chloride, and the volatile products of the reaction.

This left the sorbitol ether as a viscous, brown liquid. Analysis showed that the product averaged 2.'7 ethyl groups per molecule.

Example 2 A mixture containing 350 g. sorbitol, 1483 g. ethyl chloride, 920 g. sodium hydroxide, 100 g. water, and 2000 g. benzene was heated with stirring in an autoclave for four hours at 145-155 C. The benzene solution obtained by filtering the reaction mixture and washing the residue with benzene as in the preceding example was refluxed over absorbent charcoal for a short time and filtered. The filtrate, which was much lighter in color than the original benzene solution, was heated on a steam bath to remove the solvents. The ethyl sorbitol obtained in this way was a light reddish-brown, viscous liquid weighing 345 g. Analysis showed that the product averaged 4.6 ethyl groups per molecule.

Example 3 Example 4 A mixture of 200 g. sorbitol containing about 15% water, 900 g. benzyl chloride, 300 g. sodium hydroxide, 60 g. water, and 300 g. xylene was heated with stirring at 130440 0. for 6 hours. The mixture was then filtered. When the filtrate was subjected to fractional distillation at 15 mm. until a temperature of 275 C. was reached, about 300 g..xylene and 584 g. benzyl chloride were recovered and 34 g. benzyl alcohol, 35 g. dibenzyl ether, and 122 g. of dark, viscous residue were obtained. The residue was dissolved in 200 cc. of a benzene-alcohol mixture and heated on a steam bath with 25 g. absorbent charcoal for three hours. This mixture was filtered and the solvent was removed from the filtrate by evap- 110 oration. The benzyl sorbitol obtained as a viscous residue was light brown in color. Analysis indicated that the product consisted largely .of the monobenzyl ether of sorbitol.

The method for the preparation of the sorbitol ethers outlined in the preceding examples is capable of considerable variation. Instead of the alkyl or aryl halides, other esterification or etherification agents may be used, such as the alkyl or aryl sulfates.

When low-boiling halides are used, such as ethyl chloride, the reaction is carried out with pressure. Furthermore, the constituents of the reaction mixture may be varied considerably; for example, the percentage of diluent may be increased or decreased or the diluent may be omitted entirely. The alkyl or aryl halides may serve as the diluentsp The pressure and the period of heating are governed largely by the boiling point and reactivity of the halide employed. Alkyl and aryl sulfates may be used in place of the halides.

It is to be understood that the general method employed in the examples is not restricted to the preparation of the particular ethers cited, but is also applicable to the preparation of other alkyl and aryl ethers. Moreover, it is not limited to the production of simple ethers; mixed ethers may be prepared by reacting sorbitol with two or more halides, for example, with a mixture of ethyl and crotyl chlorides.

The present invention is concerned with those ethers of hexahydric alcohols in which the organic group replacing a hydrogen atom of a hydroxyl group of the hexahydric alcohol is a univalent hydrocarbon radical as distinguished from hydrocarbon radicals which are not univalent, as for instance hydroxy alkyl or hydroxy aryl radicals.

While I prefer to use sorbitol for the production of my improved softening agent, other six carbon atom hexahydric alcohols, such as mannitol, dulcitol, and other stereoisomers of sorbitol may be used. These ethers, and especially those of sorbitol, possess properties which make them of value as softeners or plasticizers for coating and plastic compositions. They have lower vapor pressures than the corresponding ethers derived from alcohols having a lesser number of hydroxyl groups, and this characteristic, coupled with their stability, and easy solubility in lacquer solvents, render these compounds especially valuable as plasticizing agents. They may be used with cellulose derivatives, such as cellulose nitrate, cellulose acetate, ethyl cellulose, and benzyl cellulose; and with natural and synthetic resins. sorbitol ethers may also be used in com.- positions containing oils, pigments, and other lacquer ingredients. Films containing sorbitol ethers as plasticizers are flexible and have satisfactory durability.

The following examples show the use of my new plasticizing agents in coating compositions containing cellulose derivatives and other lacque ingredients.

Example 6 Parts by weight Cellulose acetate 10 Triethyl sorbitol 3 Toluene 51 Ethyl acetate 9 Cellosolve 9 Cellosolve acetate 9 Butyl alcohol 9 Example 7 Parts by weight Cellulose nitrate 10 Crotyl sorbitol from Ex. 3 5 Ethyl acetate 40 Butyl acetate 15 Example 8 Parts by weight Cellulose nitrate 10 Benzyl sorbitol from Ex. 4 3 Ethyl acetate 25 Butyl acetate 17 Xylene 9 Example 9 Parts by weight Benzyl cellulose 10 Benzyl sorbitol from Ex. 4 3 Ethyl acetate 40 Benzene 10 Butyl acetate 20 Example 10 w e i h i Cellulose nitrate 12 Benzyl sorbitol from Ex. 4 7 Ester gum 5 Zinc oxide l5 Toluene 30 n5 Ethyl acetate 20 Butyl acetate 5 Butyl alc 6 Examples of my improved softening agents and vinyl resins are illustrated in the following three examples:

The softening agents disclosed herein are also useful in plastic compositions from which molded articles are produced.

The following example is illustrative of a composition of this character containing benzyl sorbitol as a plasticizer, gypsum as a filler, carbon as a pigment and cellulose as a binder.

, Example 14 Twenty-flve parts benzyl cellulose and 5 parts 1,cao,oos

strength and excellent gloss.

An advantage of this invention is that it provides a relatively simple means {or preparing plasticizers from sorbitol. A further important advantage resides in the fact that products of diil'erent properties, for example, products having diflerent solubilities and compatlbilities can be prepared from sorbitol by varying the etherincation reagent employed and by regulating the extent of etherincation. 1

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is tobe understood that I do not limit myself to the specific embodiments thereof except as delined in the appended claims.

I claim:

1 An ether of a six carbon atom aliphatic hexahydric alcohol in which at least one hydroxyl hydrogen is replaced by a univalent hydrocarbon radical having at least two carbon atoms, said ether being obtainable by the action of an etheritying agent on the hexahydric alcohol in the presence of an alkali.

2. An ether or a six carbon atom aliphatic hexahydric alcohol in which a plurality of the hydroxyl hydrogen atoms are each replaced by a univalent hydrocarbon radical having at least two carbon atoms, said ether being obtainable by the action or an etheriiying agent on the hexa-,

hydric alcohol in the presence or an alkali.

3. An ether or sorbitol in which a plurality of the hydroxylhydrogen atoms are each replaced by a univalent hydrocarbon radical having at least two carbon atoms, said ether being obtainable by the action of an etherii'ying agent on the hexahydric in the presence or an alkali.

4. Angether of a hexahydric alcohol selected from the class of alcohols consisting of sorbitol and rs of sorbitol in which at least one hydroxyl hydrogen is replaced by a univalent hydrocarbon radical having at least two carbon atoms, said ether being obtainable by the action 01' an etherifyins ent on the hexahydric alcohol in the presence 01' an alkali.

5. As a new compound, ethyl sorbitol obtainable by the action of an ethylating agent on sorbitol in the presence of an alkali.

6. As a new compound, benzyl sorbitol obtainable by the action of a benzylating agent on sorbitol in the presence of an alkali.

'7. Process 01' preparing an ether of a six carbon atom aliphatic hexahydric alcohol in which at least one hydroxyl hydrogen isreplaced by a univalent hydrocarbon radical having at least two carbon atoms which comprises reacting the hexahydric alcohol in the presence of an alkali under etheriiying conditions with an etherii'ying agent containing a univalent hydrocarbon radical of at least two carbon atoms.

8. Process of preparing an ether of sorbitol in which a plurality of the hydroxyl hydrogen atoms are each replaced by a univalent hydrocarbon radical having at least two carbon atoms which comprises reacting sorbitol in the presence oi an 100 alkali and under etheriiying conditions with an etheriiyins agent containing a univalent hydrocarbon radical of at least two carbon atoms.

9. Process of preparing an ether of a hexabym5 dric-alcohol selected from the class'ot alcohols consisting of sorbitol and stereoisomers oi sorbitol in which at least one hydroxyl hydrogen. is

- replaced by a univalent hydrocarbon radical having at least two carbon atoms which comprises no reacting the hexahydric alcohol in the presence of an alkali and under etheriiying conditions with an etherifying agent containing a univalent hye drocarbon radical'oi at least two carbon atoms.

10. Process of preparing ethyl sorbitol which comprises reacting sorbitol in the presence oi. an alkali and under etheriiying conditions with an ethylating agent.

11. Process oi preparing comprises reacting sorbitol in alkali and under etheritying benzylating agent.

WALTER E. LAWSON.

benzyl sorbitol which the presence or an m conditions with a i as 

